Question#1 Write a comprehensive note on all quantum mechanical system that you

have learned in the course and give analytical solution of the Schrodinger equation.
1-Free Particle:
This is the simplest one-dimensional quantum mechanical system; it corresponds to V(x)=0
for any value of x. In this case the Schrodinger equation is given by:
2
−ћ2 d ψ (x ) (1)
=E ψ (x)
2m d x 2

It can also be written as:

( )
2
d 2
2
+k ψ ( x )=0
dx

Where k2 = 2mE/ћ2 , k being the wave number. The most general solution to the Eq-1 is a
combination of linearly independent plane waves ψ +¿ ( x )=e ¿ and ψ−¿ (x )=e ¿ : ikx −ikx

ψ ( x )=A e ikx + B e−ikx

There are no boundary conditions to restrict the possible values of k and of E; the free
particle can carry any positive energy. Fixing the standard time dependence, exp(-iEt/ћ)
ћk ћk
ik (x− t) −ik (x+ t)
2m 2m
ψ ( x , t )= A e +B e ( SEQ Eq ¿ MERGEFORMAT 2 )

𝛎t) represents wave of fixed profile, travelling in the ± direction, at speed 𝛎 (an arbitrary
Now any function of x and t that depends on these variables in the special combination (x±

constant). A fixed point on the waveform corresponds to a fixed value of argument, and
hence to x and t such that
x ± νt=constant
Which is the formula for motion in the ±x direction with constant speed 𝛎. Since every point
on the waveform is moving along with the same velocity, its shape does not change as it
propagates. Thus, the first term in Eq-2 represents a wave travelling to the right and the
second term represents a wave going to the left. Since they differ by sign of the k, we might
write it as:
ћk
ik (x− t)
2m
ψ k ( x , t )= A e

k =± √
2 mE
ћ
Where k > 0(travelling ¿¿) and k < 0 ¿.
The speed of these waves is:

ν quantum =
√ E
2m
On other hand, the classical speed of a free particle is given by E=(1/2)mv2 (pure kinetic
energy, since V=0), so

ν classical =
√ 2 E =2 ν
m
quantum

This means that the particle travels twice as fast as the wave that represents it. But, the
wavefunction is not normalizable:
∞ ∞

∫ψ ¿
± ( x , t ) ψ ± ( x , t ) dx=A 2
± ∫ dx →∞
−∞ −∞

The above solutions are thus unphysical, physical wavefunctions must be square integrable.
So, we can deduce that: a free particle cannot have sharply defined momenta and energy.
It implies that solution the solution of Schrodinger equation that are physically acceptable
cannot be plane waves. Instead, we can construct physical solutions by means of linear
superposition of plane waves with help of wave packets.
∞
1
ψ ( x , t )= ∫
√2 π −∞
φ (k ) e
i(kx−wt )
dk

Where φ(k) the amplitude of the wave packet, is given by the Fourier transform of ψ(x,0) as
∞
1
φ (k )= ∫ ψ ( x , o ) e−ikx dx
√ 2 π −∞
Now, this wave packet solution suggests that momentum, the position, and energy of the
particle are no longer known exactly: only probabilistic outcomes are possible.
To summarize, a free particle cannot be represented by a single plane wave; it must be
represented by a wave packet. The physical solutions of Schrodinger equation are thus given
by wave packets, not by stationary solutions.
2- Particle near the potential wall
This system consists of a particle which is free everywhere, but beyond a point, say x=0, the
potential increases sharply. A potential of this type is known as a potential step.

{
V ( x )= 0 x <0
V 0 , x ≥0

Here we can consider two cases, depending on whether the energy of the particle is larger or
smaller than V0. First, we consider the case E> V0. The particles are free for x<0 and feel a
repulsive potential that starts at x=0 and stays constant for x>0. Let us analyze the dynamics
of this system classically and then quantum mechanically.
Classically, the particles approach the potential step or barrier from the left with a constant
momentum √ 2 mE . As the particles enter the region x ≥ 0, where the potential now is V=V0,
they slow down to the momentum √ 2 m(E−V 0 ) ; they will then conserve this momentum as
they travel to the right. Since the particles have sufficient energy to penetrate the region x≥0,
there will be total transmission: all the particles will emerge to the right with a smaller kinetic
energy E - V0. This is then a simple scattering problem in one dimension.
Quantum mechanically, the dynamics of the particle is regulated by the Schrodinger equation,
which is given in these two regions by

( )
2
d 2
2
+ k 1 ψ 1 ( x )=0 ( x <0 )
dx

( )
2
d 2
2
+ k 2 ψ 2 ( x )=0 ( x ≥ 0 )
dx

2 mE
2 2 m ( E−V 0 )
Where k 1= 2 and k 22= 2
. The most general solutions to these equations are
ћ ћ
plane waves:
i k1 x −i k 1 x
ψ 1 ( x ) =A e +B e ( x <0 )
i k2 x −i k 2 x
ψ 2 ( x ) =C e +De (x≥0)

Where A e i k x and C ei k x represent waves moving in the positive x-direction, but B e−i k x and
1 2 1

−i k x
De 2
correspond to waves moving in negative x-direction. We are interested in the case
where the particles are initially incident on the potential step from the left: they can be
reflected or transmitted at x = 0. Since no wave is reflected from the region x > 0 to the left
the constant D must vanish. Since we are dealing with stationary states, the complete
wavefunction is thus given by:
ψ ( x , t )=¿

Where A e i(k¿¿ 1 x−ωt)¿, B e−i(k x+ ωt) and C ei (k ¿¿2 x−ωt )¿ represents the incident, the reflected and
1

the transmitted waves respectively.

Let us now evaluate the reflection and transmission coefficients, R and T as defined by
reflected current density
R=
incident current density
J reflected
R=
J incident
J transmitted
T=
J incident

The incident current density is given by

iћ d ψ ¿i d ψi ( x )
J incident = (ψ i ( x ) −ψ ¿i ( x ) )
2m dx dx
ћ k1 2
J incident = A
m
Similarly, the reflected and transmitted fluxes are
−ћ k 1 2
J reflected = B
m
ћ k2 2
J transmitted = C
m
The combination of above equations yields:
2
B
R= 2
A
2
k2 C
T= 2
k1 A

The calculation of R and T is reduced to determining the constants B and C. For this we need
to use the boundary conditions of the wavefunction at x = 0. Since both the wave function
and its first derivative are continuous at x = 0.
ψ 1 (0)=ψ 2 (0)
d ψ 1 (0) d ψ 2(0)
=
dx dx
So, it implies:
 A+ B=C
k 1 ( A−B )=k 2 C

Hence
k 1−k 2
B= A
k1+ k2
2 k1
C= A
k 1 +k 2

A combination of above ratios leads to:

2
(k 1−k 2) (1− K)2
R= 2
= 2
(k 1 +k 2) (1+ K )
4 k1 k2 4K
T= 2
= 2
(k 1+ k 2) (1+ K )
k2
Where K= = √ 1−V 0 / E . The sum of R and T is equal to 1.
k1

In contrast to classical mechanics, which states that none of the particles get reflected, the
result here shows that the quantum mechanical reflection coefficient is not zero.
We see that as E gets smaller and smaller, T also gets smaller and smaller so that when E =V 0
the transmission coefficient T becomes zero and R = 1. On the other hand, when E >> V0, we
have K= √ 1−V 0 / E ≈ 1; hence R = 0 and T = 1. This is expected since, when the incident
particles have very high energies, the potential step is so weak that it produces no noticeable
effect on their motion.
3-Particle in the potential box:
Suppose

{
V ( x )= 0 ,if 0≤ x ≤ L
∞ , otherwise

A particle in this potential is completely free, except at the two ends (x = 0 and x = L), where
an infinite force prevents it from escaping. Outside the box, ψ(x) = 0 (the probability of
finding the particle there is zero). Inside the well, where V = 0, the time independent
Schrodinger equation reads:
2
−ћ2 d ψ (x )
=E ψ (x)
2m d x 2
2
=−k 2 ψ , where k = √
d ψ(x) 2 mE
Or 2
dx ћ

The above equation is the classical simple harmonic oscillator equation, the general solution
is:
ψ ( x )=A sinkx +B coskx
Where A and B are arbitrary constants and can be determined by the boundary conditions of
the problem. Normally, both ψ (x ) and dψ (x )/dx are continuous, but where the potential goes
to infinity only the first of these applies.
Continuity of ψ ( x ) requires that
ψ ( 0 )=ψ ( L )=0
⇒ ψ ( 0 ) =A sin 0+B cos 0=B
 So, B = 0, and hence ψ ( x )=A sin kx
Then ψ ( L )= A sin kL, so either A = 0 (but it leaves trivial solution) or else sin kL=0 , which
means that
kL=0 , ± π , ±2 π ,± 3 π ,. . . ..
But k = 0 and negative solutions give no physical meaning. So, the distinct solutions are
nπ
k n= , withn=1 ,2 , 3 , … … .
L
The boundary condition at x = L does not determine the constant A, but rather the constant k,
and hence the possible values of E:
2 2
ћ k n n2 π2ћ2
En = =
2 m 2 m L2

It shows that a quantum particle in the potential box cannot have just any energy but only
special allowed values. Now, to find the value of A we have to normalize the wavefunction:
L

∫ A 2 sin2 ( kx ) dx= A 2 L2 =1
0

2 2
So A =
L
Inside the well, the solutions are

ψ n ( x )=
√ 2
L
sin ⁡(
nπ
L
x)
The time-independent Schrodinger equation has delivered an infinite set of solutions, one for
each integer n. These solutions are even and odd, with respect tot the center of the well. Also,
these wavefunctions are mutually orthonormal and complete.
Question#1(a)
Compare forms of Hamiltonian for all system and point out the differences.
The general form of Schrodinger equation can be written with the help of following
arguments:
Total Energy=Kinetic energy+ Potential energy
1 2
Total Energy= m v +V
2
2
p
Total energy= +V
2m
Replacing physical observables with quantum operators; the Schrodinger equation becomes:

( )
2 2
−ћ d
+V ( x ) ψ ( x )=H ψ ( x )(1)
2 m d x2

1- Particle in Potential Box:

The potential is zero inside the box and infinite outside the walls. (Detailed article is
mentioned above). The time independent Schrodinger equation reads:

2
−ћ2 d ψ ( x )
=E ψ ( x ) (2)
2m d x 2
2- Free Particle:
In this problem the potential is zero everywhere and the particle is free to move
everywhere. The time independent Schrodinger equation reads:

2
−ћ2 d ψ ( x )
=E ψ ( x ) (3)
2m d x 2

3- Particle near the potential wall:

This system consists of a particle which is free everywhere, but beyond a point, say
x=0, the potential increases sharply. The time independent Schrodinger equation for
these two regions reads:
2
−ћ2 d ψ (x )
=E ψ (x)
2m d x 2
2
−ћ2 d ψ (x )
+V 0 ( x ) ψ ( x )=E ψ ( x ) (4)
2m d x 2

From the Schrodinger equations (2-4), we can clearly compare Hamiltonian for each
of the system. Which is changing in the following manner:
  Whenever there is no potential inside the box or even when there is no
potential at all. The Hamiltonian of the system only consists of the temporal
part of the kinetic energy.
 In case of potential a bound state appears in the solutions as stated in the
above expressions.
Question#1(b)
Compare forms of Energies and their dependence on the quantum numbers(s).
1- Particle in Potential Box:
2 2 2
n π ћ
En = 2
2ma
This is the energy for a particle in an infinite potential box. Here n states the energy levels
present inside the potential box. On increasing this value i.e. n=1,2,3,4… the energy
levels begin to rise. It also indicates that energy levels are discrete. The wave vector
results in the energy quantization.
2- Free Particle:
2 2
ћ k
E=
2m
This expression does not include n, it means there is no quantization or in other words
there is no discretization. It clearly depicts that we have no boundary conditions which yields
all the solutions of equation.
3- Particle near the potential wall:
In the region where the potential is zero, the particle behaves like a free particle, so the
energy appears to be continuous and the Schrodinger equation yields all solutions. Which
means there is no quantization. Whereas, in the bounded region (where potential is present)
the quantization will paly its role.
Question#1(c)
Compare forms of wavefunctions and their dependence on the quantum numbers(s).
1- Particle in Potential Box:

ψ n ( x )=
√ 2
L
sin ⁡(
nπ
L
x)

The wavefunction consists of ‘sin’ part which indicates that the solution is oscillatory. ‘n’
depicts we will have discrete values rather than continuous. Also, the solutions will be
alternative with respect to the center of potential box, mutually orthonormal and complete.
2- Free Particle:
∞
1
ψ ( x , t )=
√ −∞
2 π
∫ φ (k ) e
i(kx−wt )
dk

Here the solution is not oscillatory but rather a travelling one, as it has no boundaries. The
exponential factor justifies the argument stated. It carries a range of energies and speeds
therefore it is known as wave packet.
4- Particle near the Potential wall:
The complete wavefunction of this system given by
ψ ( x , t )=¿
the first region where the potential is zero, the wavefunction has similar attributes like free
particle and in the second region it behaves like trapped particle. But apparently these
solutions do not depend upon quantum numbers.
Question#1(d)
Besides energy compare at least one more expectation value and its operator form for
all solutions.
 Particle in Potential Box:
 Expectation value of energy:

ψ n ( x )=
√ 2
L
sin ⁡(
nπ
L
x)

⟨ | | ⟩
2 2
nπx −ћ d nπx
sin ⁡( ) 2
sin ⁡( )
L 2m d x L
En =
⟨ sin ⁡(
nπx
L |
) sin ⁡(
nπx
L
) ⟩
⟨ | ⟩
2
nπx d nπx
sin ⁡( ) 2
sin ⁡( )
−ћ2 L dx L
En =
2m
⟨ sin ⁡(
nπx
L
) sin ⁡( |
nπx
L
) ⟩
⟨ | ⟩
2
nπx nπ nπx
2
sin ⁡( ) −( ) sin ⁡( )
−ћ L L L
En =
2m
⟨ sin ⁡(
nπx
L |
) sin ⁡(
nπx
L
) ⟩
En =
2
ћ nπ
( )
2 ⟨ sin ⁡( |
nπx
L
) sin ⁡(
L⟩
nπx
)

2m L
⟨ sin ⁡(
nπx
L
)|sin ⁡(
L ⟩
nπx
)

2 2
ћn
En = 2
8m L
 Expectation value of momentum:

(√ ) (√ )
L ¿
d ⟨x⟩ 2 nπx 2 nπx
⟨ p ⟩=m ⟨ x ⟩=∫ sin ⁡( ) x sin ⁡( ) dx
dt 0 L L L L
L

a 0
(
⟨ x ⟩= 2 ∫ x . sin 2 ⁡( πx ) dx
L )
L
⟨ x ⟩=
2

⟨ p ⟩=m d L =0
dt 2 ()
2- Free Particle:

 Expectation value of energy:

Let us consider a simple form as an oscillating function: φ ( x )=cos ( kx ) and now
calculate expectation value of energy operator:

⟨ | ⟩
2
−ћ2 d φ(x )
φ (x)
2m d x 2
E=
⟨ φ(x )|φ(x )⟩

⟨ | ⟩
2
d cos ( kx )
cos ( kx )
−ћ2 d x2
E=
2m ⟨ cos ( kx )|cos ( kx ) ⟩
−ћ ⟨ cos ( kx )|−k cos ( kx ) ⟩
2 2
E=
2 m ⟨ cos ( kx )|cos ( kx ) ⟩
ћ 2 k 2 ⟨ cos ( kx )|cos ( kx ) ⟩
E=
2m ⟨ cos ( kx )|cos ( kx ) ⟩
2 2
ћ k
E=
2m

 Expectation value of momentum:

Let us consider the initial wavefunction of a free particle is:φ ( x )=cos ( kx )
and now calculate expectation value of momentum operator:

⟨ p ⟩=
⟨ |
φ ( x ) −iћ φ (x)
dx
d
⟩
⟨ φ ( x)|φ ( x)⟩

⟨ p ⟩=
⟨ | d
cos ( kx ) −iћ cos ( kx )
dx ⟩
⟨ cos ( kx )|cos ( kx ) ⟩
⟨ p ⟩=i ћ k
⟨ cos ( kx )|sin ⁡(kx )⟩
⟨ cos ( kx )|cos ( kx ) ⟩
⟨ p ⟩=ћk
Question#3
Discuss the importance of approximation methods to solve the Schrodinger equation.
Most problems encountered in quantum mechanics cannot be solved exactly. Exact solutions
of the Schrodinger equation exist only for a few idealized systems. To solve general
problems, one must resort to approximation methods. Here we focus on two approximation
methods: Perturbation theory and the variational method.
Perturbation theory assumes that the problem we wish to solve is, in some sense, only
slightly different from a problem that can be solved exactly. In the case where the deviation
between the two problems is small, perturbation theory is suitable for calculating the
contribution associated with this deviation; this contribution is then added as correction to the
energy and the wavefunction of the exactly solvable Hamiltonian. So, perturbation theory
builds on the known exact solutions to obtain approximate solutions.
If a Hamiltonian of system cannot be reduced to an exactly solvable part plus a small
correction, then we may consider the variational method or the WKB approximation. The
Variational method is particularly useful in estimating the energy eigenvalues of the ground
state and the first few excited states of a system for which one has only qualitative idea about
the form of the wavefunction.
The application of the approximation methods to the study of stationary states consists of
finding the energy eigenvalues En and the eigenfunctions of time-independent Hamiltonian
that does not have exact solutions.
Question#4
Write a short personal statement about the most surprising or exciting element that you
learned about in the course.
The most surprising facts I have learned in this course is about particle in a potential box. The
expression of energy is given as:
2 2 2
n π ћ
En = 2
2ma
Where n=1,2,3,4…
Strange! A particle bound to a one-dimensional box can only have certain discrete(quantized)
values of energy. Further, the particle cannot have a zero kinetic energy i.e. it is impossible
for a particle bound to a box to be “at rest”.
Since, it deviates from the concept of continuous energy which originates form classical
Physics. That’s why it is very surprising element.